Tall oil esters



Patented Jan. 3, 1 950 TALL OIL ESTERS Sylvan Owen Greenlee, Louisville,Km, assignor to Devoe & Raynolds Company, Inc., Louisville, Ky., acorporation of New York No Drawing. Application April 10, 1946, Serial,No. 661,061

4 Claims. 1

The invention relates to new synthetic drying compositions and moreparticularly to tall oil acid esters of high molecular weight resinouspolyhydric alcohols.

The-new drying compositions are valuable drying varnish compositionshaving improved properties, including improved resistance to alkali,water and chemicals, improved hardness and flexibility, improved dryingproperties, improved body, gloss and adhesion to surfaces, and otherdesirable properties as compared with tall esters of ordinary alcohols.

The new synthetic drying compositions ofthe present invention in whichthe high molecular weight resinous polymeric polyhydric alcohols areused and esterified with tall oil acids enable drying varnishes to beobtained from acids which would not give drying varnishes whenesterified with glycerol, penta-erythritol and the like due to the lowunsaturation present in the acids.

The new drying compositions enable films of acceptable flexibility to beobtained even though the oil portion of the resulting varnish is verylow. Tall oil contains around 40 to 50% resin acids and the polymericpolyhydric alcohols used for esteriiying the tall oil acids is resinousin nature; and these resinous alcohols appear to contribute to theflexibility as well as the hardness.

Tall oil is available as a cheap waste product or by-product of thepaper pulp and when used with ordinary alcohols to form esters does notgive valuable drying varnishes; but when esteritied with the polymericpolyhydric alcohols according to the present invention excellentvarnishes are obtained.

Tall oil is low in unsaturation and gives low bodied products whenesterified with ordinary alcohols; but when esterified with the highmolecular weight resinous polymeric'polyhydric alcohols according to thepresent invention hig bodied products can be obtained.

In addition, valuable composite products can be obtained in which thetall oil esters of the resinous high molecular weight polymericpolyhydric alcohols are combined with other esters.

The new synthetic drying compositions are made by the esterificationwith tall oil acids of high molecular weight resinous polyhydricalcohols and more particularly of high molecular weight polymericpolyether polyhydric alcohols which are polyether derivatives ofpolyhydric phenols having hydroxyl-containing aliphatic radicals unitedto the phenolic residues through ether linkages. Such high molecularweight polyhydric alcohols can readily be made of semisolid or solidconsistency and of high molecular weight.

- The high molecular weight resinous polyhydric alcohols which aresubjected to esterification to produce the new esters, areadvantageously prepared by the reaction of polyhydric phenols withpolyhalo alcohols, epihalohydrins, or polyepoxide compounds to formcomplex reaction products containing several alcoholic hydroxyl groupsper molecule. In certain cases the halohydrins or epoxy compounds usedin making the polyhydric alcohols introduce epoxy groups as well asalcoholic hydroiwl groups into the high molecular weight product to giveproducts which are hydroxy-epoxy products containing a plurality ofalcoholic hydroxyl groups and one or more epoxy groups. For purposes ofesterification epoxy groups when present act for the most part as glycolgroups in reaction with organic acids, one epoxide group being ingeneral equivalent to two alcoholic hydroxyl groups. The production ofvarious high molecular weight polyhydric alcohols suitable for use inmaking the new drying compositions of the present invention is describedin my prior applications Serial Nos. 502,317, filed September 14, 1943now Patent No. 2,456,408, 535,342, filed May 12, 1944, 617,176 and617,178, filed September 18, 1945, 626,449, filed November 2, 1945, and621,856, filed October 11, 1945.

In my prior applications Serial Nos. 502,317, 535,342 and 617,178 I havedescribed the preparation of polyhydric alcohols derived by the reactionof polyhydric phenols with polyhalohydrins, epihalohydrins, andpolyepoxides both without and with the use of monofunctional reactants.By regulating the quantities and proportions of the reactants complexreaction products of predetermined molecular weights and predeterminedhydroxyl contents can be obtained. Where chlorhydrins such asepichlorhydrin, glycerol dichlorhydrin or glycerol monochlorhydrin areused the reaction is carried out in the presence of caustic soda equalto or somewhat in excess of the amount required to combine with all ofthe halogen of the halohydrin. Such complex polyhydric compositions andparticularly such compositions as are solid at ordinary temperature andthose of much higher melting point are useful in the preparation of thenew drying compositions of the present invention. With certain of thecomplex polyhydric compositions, it is advantageous to have at leastfive to fifteen esterifiable groups per molecule. This number ofhydroxyl groups are especially advantageous when last dryingcompositions are to be prepared. By at least flve esteriflable groups ismeant at least hydroxyl groups in which one epoxide group is consideredtobe the equal of two hydroxyl groups. On the other hand, there arecases where complex polyhydric compositions -of relatively high meltingpoint, containing as low as two or three hydroxyl groups, may beesterifled with tall oil acids to give compositions which may bedissolved in solvents to give valuable i'ast drying varnishes. v

In my prior application Serial No. 617,176, filed September 18, 1945, Ihave further described complex reaction products of polyhydric phenolswith polyfunctional halohydrins such as epichlorhydrin such asepichlorhydrin and glycerol dichlorhydrin with the difunctionalchlorhydrin used in proportions in excess of that equivalent to thepolyhydric phenol and less than twice the equivalent amount, with theaddition of caustic alkali equal to or somewhat in excess of the amountrequired to combine with the halogen of the halohydrin and givingcomplex polymeric products containing both epoxy groups and hydroxylgroups. Such complex polymeric epoxy-hydroxy products and compositionsare also advantageously used for reaction with tall oil acids to formthe new drying compositions of the present invention. The complexepoxy-hydroxy compositions of my prior application Serial No. 621,856,flied October 11, 1945, can similarly be In my companion application,Serial No. 626,449, flied November-2, 1945, I have described newpolyepoxy products and compositions obtained by the direct addition ofpolyhydric phenols and polyepoxides, with the proportion of polyepoxidesused in excess 01' the equivalent amount so that the resulting reactionproducts contain epoxy groups. Such polyepoxy reaction products andparticularly those which are solids atroom temperature areadvantageously used in making the new drying compositions of the presentinvention.

The polyhydric alcohols used, regardless of the method of theirproduction, are advantageously solids at ordinary temperature and inmany cases products of much higher melting point are desirable. Thepolymeric polyhydric alcohols produced by the reaction of polyhydricphenols and polyfunctional aliphatic reactants such as polyhalohydrins,epihalohydrins and polyepoxides are complex reaction products but ingeneral, and assuming a straight line reaction and polymerization, theycontain alternating aromatic nuclei.

from the polyhydric phenol and aliphatic hyroxyl containing nucleiunited through ether linkages. When an excess of polyhydric phenol isused some of the phenolic hydroxyl groups may be present in the finalproduct, and products con-.

taining such terminal phenolic hydroxyl groups can be used foresteriflcation. In general, however, I consider it more advantageous touse polymeric polyhydric alcohols which are free or relatively free fromterminal phenolic hydroxyl groups and which contain instead eitherterminal non-reactive groups or terminal hydroxyl-containing orepoxy-containing groups. I

v In such polymeric products made from polyhydric phenols withpolyfunctional halohydrins, epihalohydrins and polyepoxides there willin general be one or more alcoholic hydroxyl groups between the phenolresidues and there may also be terminal alcoholic hydroxyl groupsorepoxy mumj High melting and high molecular weight products' containinga lesser number of hydroxyl groups may be produced e. g., by usingmixtures of dichlorhydrinsbr epichlorhydrins with dichlorides such asdichlordiethyl ether or dichlorbutene.

Such dichlorides will give intermediate aliphatic groups between thephenolic residues which do not contain esteriflable hydroxyl groupswhile the residues formed from the dichlorhydrins or epichlorhydrinswill contain esterifiable hydroxyl groups. Similarly products obtainedby the reaction of polyhydric phenols with such dichlorides, using thepolyhydric phenols in excess, and reacting the resulting complexpolyhydric phenols with simple polyepoxides, will give high meltingpoint products having a limited number oi. hydroxyl and epoxy groups.

The high molecular weight resinous polyhydric alcohols have alternatingaliphatic chains and aromatic nuclei united through ether oxygen and aretree from functional groups other than epoxy and hydroxyl groups.

The new synthetic drying compositions of the present invention areprepared by esteriflcation of such high molecular weight polyhydricalcohols or epoxy-hydroxy compositions with tall 011 acids either aloneor admixed with other acids such as unsaturated vegetable oil acids.

Esteriflcation of the complex high melting point polyhydric alcohols andepoxy-hydroxy compounds can conveniently be carried out by heating toelevated temperatures either with or without the addition of a catalystand under conditions promoting the removal of water of reaction, e. g.,by bubbling a slow stream of inert gas such as carbon dioxide throughthe reaction mixture while heated to elevated temperatures or by the useof a small amount of water insoluble solvent with the use of a suitablereflux condenser for removing the water.

The preparation of the new synthetic drying composition by theesterlfication of tall oil with the high molecular weight polyhydricalcohols and epoxy hydroxides will be illustrated by the followingexamples, but it will be understood that the invention is not limitedthereto. The parts are by weight.

Example L-The high molecular weight poly hydric alcohol used was made asfollows: Into a 300 gallon open kettle, equipped with a mechanicalagitator was weighed 866 lbs. of water, 392 lbs. of bis-phenol, lbs. ofcaustic soda, and the resulting mixture was agitated until thebis-phenol had all dissolved in the aqueous alkali. The temperature atthis stage was 40 C. To this solution was added 185 lbs. ofepichlorhydrin and with continuous agitation the temperature was raisedto 70 C. At this point 20 lbs. of caustic soda dissolved in 20 lbs. ofwater was added to the reaction mixture and the temperature wasgradually raised to 93 C. and held at 93 to C. tor/1 hour. At the end ofthis reaction period the upper salt water layer' was removed from thelower tafl'y like resin layer by decantation. About 65 gallons ofboiling water was added and the resin mixture was agitated for 15minutes and the water layer was again removed. The

washing was repeated four times, adding enough.

added 312 parts of crude tall oil containing about 45% resin acids. Thereaction mixture was heated with continuous agitation and while bubblingcarbon dioxide through the mixture for three hours at 250 C. to given anacid value below 1. v

A 35% solution of this product, when treated with 0.05% cobaltnaphthenate (based on the varnish solids) gave films of 0.003 inch whichair dried to tack-free products in one hour.

Example II.-By a similar procedure as that used in preparing thepolyhydric alcohol used -in Example I a hydroxy-epoxide was preparedfrom four mols of bisphenol, 5 mols of epichlorhydrin and 6.3 mols ofsodium hydroxide, the reaction going from 40 to 100 C. in 80 minutes andbeing kept at 100-104 for sixty minutes. The resulting resin afterwashing and drying had a softening point of 100 C.

To 200 parts of the hydroy-epoxy resin so produced was added 322 partsof a refined tall oil containing about 35% resin acids. The mixture .washeated at 250 C. in accordance with the procedure of the precedingexample until an acid value of i2 was obtained.

A 50% solution of this product in mineral spirits had a viscosity of D.When treated with driers this product gave films which air dried in 24hours to give a hard, flexible product.

Example III .--By the same procedure as that used in preparing thepolyhydric alcohol used in Example I, a polyhydric alcohol was preparedby the reaction of mols of bisphenol with 15.5 mols of epichlorhydrinand 9 molsof glycerol monochlorhydrin in the presence of 24.54 mols ofsodium hydroxide and had a softening point of 116 C. a

In a vessel provided with a mechanical agitator and with a refluxcondenser of the Bidwell- Sterling type was placed 183 parts of thepolyhydric alcohol and 315 parts of crude tall oil. A sufllcient amountof mineral spirits was added to give refluxing when heated at 50 C. Thisreaction mixture was heated with continuous agitation for one hour at250 C., two hours at 260 C. and held at 270 C. until the acid value hadreached 8.5.

To the resulting product was added 0.05% eabalt drier and an equalweight of hydrocarbon solvent and 0.003 inch films were spread. Thesefilms baked for minutes at 150 C., or air-dried overnight, gave a hard,flexible fllm.

It is sometimes desirable to increase the ratio of long chain acidesters to resin esters present in the new tall oil compositions,especially where crude tall oil containing 40-50% resin acids are used.This may be advantageously done by using unsaturated acids or theiresters in connection with tall oil, as illustrated by the followingexamples.

Example IV.-In avessel provided with a mechanical agitator and acondenser of the Bidwell- Sterling type was placed 280 parts of the samepolyhydric alcohol referred to in Example I and 315 parts of crude talloil. Sufllcient mineral spirits was added to give refluxing when heatedat 270 C. The reaction mixture was heated with continuous agitation andat 270 C. for about six hours and 40 minutes to give a product with anacid value of 7.8. After cooling the mixture to 200 C. 505 parts of Rbodied linseed oil were added and the resulting mixture heated withagitation for 45 minutes at 250 C.

The resulting product when dissolved in hydrocarbon solvents and treatedwith driers gave excellent varnishes.

Example V.In an apparatus such as referred to inthe preceding examplewere placed 280 parts of the same polyhydric alcohol used in Example I,236 partsoi' crude tall oil, and 63 parts of linseed oil acids.Sufllcient mineral spirits was added to give refluxing at 250 C. and thereaction mixture was heated at that temperature for 12 hours to give aproduct with an acid value of 10.

A 50% solution of the product in mineral spirits had a viscosity of Z-2and when treated with driers gave an excellent varnish.

E-tample VL-A mixture of 280 parts of th same polyhydric alcohol used inExample 1, 157.5 parts of crude tall oil and 126 parts of linseed oilacids'were heated-to eil'ect esteriilcation in accordance with theprocedure described in the preceding example with heating at 250 C.until an acid value of 6.5 was obtained.

A 50% solution of the resulting product in mineral spirits had aviscosity of Z-3 and with driers gave an excellent varnish.

The high molecular weight polyhydric alcohols of the above examples areof the type containing at least five esteriflable groups per moleculeand within the range of 5 to 15 esterifiable groups per molecule, suchesteriflable groups including hydroxyl groups and epoxide groups (oneepoxide being the equal of two hydroxyl groups). Such polyhydricalcohols are esterified with an average of at least five ester groupsper molecule of polyhydric alcohol.

In the above examples the proportions of high molecular weight polymericpolyhydric alcohol esterifled to tail oil acids used for esteriflcationvaries from about 1.8 to 1 to about 1 to 1.7 by weight. In Examples I toIII in which the tall oils are used alone with the high molecular weightresinous alcohols the proportions vary from about 1.6 to 1 to about 1 to1.7. In Examples V and VI the proportion of resinous alcohol to tall oilis from about 1.2 to l to about 1.8 to 1 and the proportion of dryingoil acids is from about 22% the weight of the resin to about 44% theweight of the resin.

Other resinous polymeric polyhydric alcohols such as described in saidprior applications can similarly be used and esterifled with tall oilacids to give new drying. compositions. Thus, polymeric polyhvdricalcohols containing a number of intermediate hydroxyl groups and whichdo not contain terminal hydroxyl groups can be esterified; as-well aspolymeric polyhydric alcohols which contain terminal hydroxyl groups orterminal epoxide groups or both terminal hydroxyl and epoxide groups. asdescribed in said prior applications.

The present invention provides improved tall oil esters which arevaluable drying varnish compositions even i'rom tall oil acids ofrelatively low unsaturation. The presence of a number of hydroxyl groupsin the polymeric polyhydric a1- cohols enables an increased number ofester groups to be'united to a. single alcohol molecule and enablesimproved drying varnishes to be obtained even from tall oil acids ofrelatively low unsaturation. The resinous nature of the high molecularweight polymeric polyhydric alcohols, including polymeric alcohols whichare hydroxy epoxides. appears to play an important part in giving to thenew drying ester compositions their valuable drying and otherproperties, such as those previously referred to.

I claim:

1. A synthetic drying composition consisting essentially of tall oilesters of a high molecular weight resinous polymeric poiyhydric alcoholhaving an average of more than five esteriflable groups per molecule,said resinous polymeric polyhydric alcohol being a polyether derivativeof a dihydric phenol having alternating aliphatic chains and aromaticnuclei united through ether oxygen and being free from functional groupsother than epoxy and hydroxyl groups. the proportions of tall oilcombined with the high molecular weight polymeric polyhydric alcoholsbe:- ing from about 1.7 to 1 to about 1 to 1.8 by weight.

2. A synthetic drying composition as defined in claim 1, in which theresinous polymeric polyhydric alcohol is also esterified with from about22 per cent to 44 per cent its weight of vegetable drying oil acids. I

3. A synthetic drying composition as defined in claim 1, in which saiddihydric phenol is 4,4- dihydroxydiphenyl-2,2-propane and in which saidaliphatic chains are derived from epichlorohydrin.

4. A synthetic drying composition as defined in claim 1, in which theresinous polymeric polyhydric alcohol is also esterified with from about22% to 44% its weight of vegetable drying oil 8 acids, in which saiddihydric phenol is '-dihydroxydiphenyl-2,2-propane and in which saidallphatic chains are derived from epichlorohydrin.

SYLVAN OWEN GREENLEE.

REFERENCES CITED The following references are of record in lthe file ofthis patent:

UNITED STATES PATENTS OTHER REFERENCES Paint, Oil and Chemical Review,Nov. 2, 1944 (pages 84-86).

1. A SYNTHETIC DRYING COMPOSITION CONSISTING ESSENTIALLY OF TALL OILESTERS OF A HIGH MOLECULAR WEIGHT RESINOUS POLYMERIC POLYHYDRIC ALCOHOLHAVING AN AVERAGE OF MORE THAN FIVE ESTERIFIABLE GROUPS PER MOLECULE,SAID RESINOUS POLYMERIC POLYHYDRIC ALCOHOL BEING A POLYETHER DERIVATIVEOF A DIHYDRIC PHENOL HAVING ALTERNATING ALIPHATIC CHAINS AND AROMATICNUCLEI UNITED THROUGH ETHER OXYGEN AND BEING FREE FROM FUNCTIONAL GROUPSOTHER THAN EPOXY AND HYDROXY GROUPS, THE PROPORTIONS OF TALL OILCOMBINED WITH THE HIGH MOLECULAR WEIGHT POLYMERIC POLYHYDRIC ALCOHOLSBEING FROM ABOUT 1.7 TO 1 TO ABOUT 1 TO 1.8 BY WEIGHT.